Polarimetry: Acid Catalyzed Sucrose Decomposition

Nathaniel J Zhu
Department of Chemistry and Biochemistry, George Mason University
Received: March 6, 2014: In Final Form: March 20, 2014

Keywords: Sucrose polarimetry, Polarimetry, Biot's Law, rate equation.

ABSTRACT: This report demonstrated the kinetic relationship between optical activity () and concentration of a sucrose reaction
to glucose and fructose catalyzed by hydrochloric acid. Kinetic properties were studied using a LabQuest polarimeter to discover
the angle of rotation at a reference point (first maxima after angle 0) which was used to calculate concentration and subsequently
the rate order of the reaction. The specific rotation of sucrose in 15% and 30% sucrose solutions were found to be 82.1 0.0229
and 70.4 0.0151 respectively. The percent error of 30% and 15% sucrose specific rotation was 5.83% and 23.5% respectively.
The reaction order was determined to be 1st order. The calculated rate constant was 0.092132 of the reference rate constant,
0.1162 min-1 with an error of 20%.
Introduction
Polarimetry is the study of a chemical's optical
activity by measuring its rotation. Polarimetry could also be
used to study the kinetics of certain optically active chemicals
because there is a relationship between change in
concentration and optical activity as a chemical reaction
proceeds (Colby, 2014). When sucrose is added to water, it
slowly breaks down however sucrose breaks down much
quicker in the presence of an acid catalyst such as
hydrochloric acid (HCl).
As hydrochloric acid is breaking down the sucrose,
the rate is being recorded by the polarimeter in the form of
optical activity which can be converted into concentration
using biot's law.
Equation 1.1: Biot's Law

Biot's law presents the conversion between optical actvity
and concentration where is the optical activity, *+ is the
specific rotation in degrees (dm-1mLg-1), l is the length of the
cell (dm), and c is the concentration (g/ml) (Colby 2014).

Equation 1.2: Specific Angle

The water also has optical activity however this experiment's
goal is to measure the optical activity of sucrose therefore,
the actual optical activity is the optical activity of the
sucrose/water mixture mixus the optical activity of the pure
water (ResearchGate, 2014).
Equation 1.3: Rate of a Reaction

The rate of a chemical reaction where r is the rate, [A] is the
concentration, x is the rate order, and k is the rate constant .
x varies for different reaction orders (a first order reaction
would equal to 1). Integrating the first order rate law gives
equation 1.4 (Colby 2014).
Equation 1.4: Integrated first Law Rate Equation

To determine whether a trend is 0th, 1st, or second order,
three plots of [A] vs t, ln[A] vs t, and 1/[A] vs time needs to be
plotted. The graph that is linear is the corresponding order of
the reaction. [A] is the concentration, k is the rate constant,
and t is the time (Colby 2014).
Equation 1.5: Exponential Decay Equation

The inverse of the rate law gives the decay equation where
[A] is the final concentration, [A]
0
is the initial concentration,
k is the rate constant, and t is the time (colby, 2014).



Figure 1.3: Break down of Sucrose

The primary goal of this experiment was to
determine the kinetic properties of sucrose 30% and 15%
from its relationship with optical activity. This was
accomplished using calibration reactions, time interval
recordings, and conversion equations.


Experimental
I. Equipment Setup
This experiment used concentrated 6M hydrochloric
acid in part 2 so a lab coat with gloves were worn and this
reaction was performed in a fume hood. First, the vernier
labquest device was obtained along with the polarimeter.
The polarimeter contained two cables which was plugged into
two different locations on the device (there was no possibility
of mixing up the connection. The wrong plug won't fit the
cable). Next, the mass of sucrose was weighed and prepared
in a 100 mL volumetric flask. Two 100 mL volumetric flaskes
were filled with 30 g and 15g of sucrose respectively using a
glass funnel, and then washed down using water such that
the volume of each was 100 mL. In LabQuest, a new file was
opened and a water blank was obtained by filling the
polarimeter cell to 10 cm 0.1cm and placing the cell back
into the polarimeter. On top of the polarimeter there was a
spinning knob that was turned in order to create a plot of
illumination vs. angle. LabQuest was switched to graph view
and the record button was pressed at the same time the
polarimeter knob was turned clockwise (or counterclockwise)
at a slow but steady rate for a default time of 15 seconds.
After 15 seconds, the plot of illumination vs. angle will be
displayed on LabQuest. The water blank was the first angle
which illumination first peaked at. The peak was determined
by taking a Gaussian curve using the "curve fit" feature of
LabQuest. Alternatively for a slightly less accurate but much
quicker method, the angle was estimated by simply clicking
the point at the highest illumination which also displayed the
corresponding angle. Finally, the data was saved into
LabQuest. The blank was repeated three times. The water
blank was rinsed out and then the sucrose angles were
measured.
II. Part 1: Sucrose Specific Rotation
Earlier, 30g and 15g of sucrose was massed and
placed into two 100 mL volumetric flasks to produce two 100
mL volumetric flasks. Beginning with the flask containing 30%
sucrose solution, volume was added until the height of the
cell was 10 cm. The same method of collecting Illumination
vs. angle used for the blank was applied for the optically
active sucrose. Again the record button was pressed as the
wheel was turned simultaneously to obtain a plot. The angle
was obtained using a gausian plot for the first peak. This
processes was repeated two more times for a total of three
trials. The cell containing the 30% sucrose solution was
recycled back into the volumetric flask. Next, the solution
containing 15% sucrose was added to the polarimetry cell and
again the angle at the first peak was obtained three times and
saved.
III. Part 2: Sucrose kinetics in the presence of Acid
In part 1, the kinetics of sucrose without acid was
studied and in this part, an acid was added to the sucrose and
the kinetics was studied and compared. In this part of the lab,
6M HCl was mixed with each sucrose solution and the angle
was obtained every 2 minutes for 1 hour. This reaction was
time specific since the reaction was ongoing. Initially, the
polarimeter was setup and calibrated as in part 1. In the
calibration step, volume of solution added however was
different than part 1. In part 1, the volume added was
whatever to fill up to a height of 10 cm however in part 2, 20
mL of sucrose solution was added. Data collection was
collected once for each sucrose solution.
After the calibration step, the next is to create a
sucrose solution with acid in the cell. A 10 mL of concentrated
6M HCl was added to 10 mL of 30% sucrose in a beaker and
then transfered to the polarimeter cell with height recorded
to 0.1 cm. Next, the LabQuest was set to time based for 2
minutes. The record button was pressed simulataneously as
the polarimeter knob was rotated clockwise (or whichever
direction was used for previous steps). The recorded data was
stored and the angle was recorded every 2 minutes for 1
hour.





Results and Discussion
The kinetic properties of sucrose breakdown to glucose and
fructose catalyzed by HCl was indentified and the rate order
was determined.
Overall, the rate was determined by the pattern
which the data is expressed. The graph of concentration vs.
time was curved such that the change in concentration of
sucrose as time increased decreased. Taking the natural log of
an exponential decrease to give a linear graph meant that the
chemical reaction was a first order.
Table 2.1: Specific Rotation

LabQuest was used to obtain the optical activity of
water (blank). The angle of rotation was equal to the total
rotation - the rotation of water, the specific rotation is the
rotation of 15% and 30% sucrose divided by the height in dm.
The %difference of the specific rotation was 23.5% different
than the literature value of 66.5. The error in the confidence
interval of the 15% sucrose solution was determined to be
small at 0.0229 so the data was precise and the 30% solution
also had a low confidence interval. The specific rotation for
the 30% was more accurate with a % difference of 5.83%.
Figure 1.1:

The HCl was mixed with the sucrose solution and the
angle of the nearest maximum peak was obtained every 2
minutes for an hour using a gausian fit on LabQuest. The
angles were converted to specific rotation (table 2.1) which
was then used to obtain the concentration of sucrose (mol/L)
using biot's law again. The concentration of sucrose was
plotted against time to obtain a curved plot. This pot
indicates that concentration of sucrose decreased
exponentially until it asymptoted near zero. Conceptually, this
mean that initally, the catalyst was able easily access and
catalyze the reaction whereas later the solution was so dilute
with product and so little reactant that very little sucrose was
further broken down. The R^2 value was 0.923 which meant
that the exponential fit was good.
Figure 1.2: Summary of values calculated from ln(K) vs. 1/ plot

The graph of concentration vs. time was not linear
so indicated that the graph at least was not zeroth order. The
graphs of natural log of concentration and 1/[concentration]
of sucrose was obtained and the graph of ln[concentration]
appeared linear. This meant that the reaction was first order.
The R^2 value was 0.947 which indicates good linear fit.
Table 4: LINEST Output
slope
-
0.092132
-
0.540854 y-intercept
error in
slope 0.007297 0.106082 error in y-in
R
2
0.947158 0.194532 s(y)
The LINEST output revealed the slope to less uncertainty than
the plot. In addition, the error values of slope was only
0.007297 which is very low. The y-intercept had a higher
error at about 20%.
The 95% confidence interval of the slope was 0.016273 and
the 95% confidence interval of the y-intercept was 0.236563
from the mean.




y = 0.5659e
-0.088x

R = 0.9234
0.000
0.200
0.400
0.600
0.800
1.000
0 10 20 30
[
S
u
c
r
o
s
e
]

(
m
o
l
/
L
)

Time (min)
y = -0.0925x - 0.541
R = 0.9473
-3.500
-3.000
-2.500
-2.000
-1.500
-1.000
-0.500
0.000
0.500
0 10 20 30
L
n
(
[
S
u
c
r
o
s
e
]

(
m
o
l
/
L
)
)

Time (min)

Table 2.2: Table of concentration, rates, and error
The recorded data for the first hour of the sucrose/hcl
reaction after having been converted into concentration from
optical activity so that reaction velocity/rate could be plotted
(figure 1.1 and figure 1.2). Error was small throughout. The
slope of the natural log of sucrose concentration had a
negative slope which confirmed that the reaction was an
exponential decay.









Table 2.3: Table 2.2 continued

Time
(min)
[Sucrose]
mol/ L
Error
Reaction
Rate
mol/L/min Error
0 0.877 - -
2 0.468 1.01E-04 0.0343 1.32E-04
4 0.400 8.59E-05 0.0548 1.06E-04
6 0.290 6.24E-05 0.0426 7.64E-05
10 0.205 4.41E-05 0.0149 5.40E-05
12 0.145 3.12E-05 -0.0086 4.69E-05
14 0.163 3.49E-05 0.0255 4.24E-05
16 0.112 2.40E-05 0.0048 3.25E-05
18 0.102 2.19E-05 0.0056 2.94E-05
20 0.091 1.95E-05 -0.0054 2.93E-05
22 0.102 2.19E-05 0.0084 2.85E-05
24 0.085 1.83E-05 -0.0028 2.67E-05
26 0.091 1.95E-05 0.0028 2.67E-05
28 0.085 1.82E-05 -0.0153 3.08E-05
30 0.115 2.48E-05 0.0145 3.10E-05
32 0.086 1.86E-05 -0.0002 2.63E-05
34 0.087 1.87E-05 0.0079 2.41E-05
36 0.071 1.53E-05 -0.0026 2.24E-05
38 0.076 1.64E-05 -0.0019 2.38E-05
40 0.080 1.72E-05 0.0092 2.17E-05
42 0.062 1.32E-05 -0.0067 2.09E-05
44 0.075 1.61E-05 -0.0142 2.74E-05
46 0.103 2.22E-05 0.0123 2.79E-05
48 0.079 1.69E-05 0.0046 2.26E-05
50 0.070 1.50E-05 -0.0010 2.15E-05
52 0.072 1.54E-05 -0.0016 2.23E-05
54 0.075 1.61E-05 -0.0026 2.36E-05
56 0.080 1.72E-05 -0.0050 2.60E-05
58 0.090 1.94E-05 0.0075 2.53E-05
60 0.075 1.62E-05 0.0377 1.62E-05
Time
(min)
[Sucrose]
Exponential
Decay Error
Reaction
Rate
(mol/L/m
in) Error
ln
[Sucrose]
0 - - - -0.132
2 0.507 0.0759 0.0434 0.0985 -0.768
4 0.420 0.0629 0.0359 0.0817 -0.884
6 0.348 0.0521 0.0272 0.0632 -1.222
10 0.239 0.0358 0.0205 0.0465 -1.640
12 0.198 0.0297 0.0170 0.0385 -1.849
14 0.164 0.0246 0.0141 0.0319 -1.837
16 0.136 0.0204 0.0117 0.0265 -2.032
18 0.113 0.0169 0.0097 0.0219 -2.205
20 0.094 0.0140 0.0080 0.0182 -2.252
22 0.078 0.0116 0.0066 0.0151 -2.518
24 0.064 0.0096 0.0055 0.0125 -2.675
26 0.053 0.0080 0.0046 0.0104 -2.402
28 0.044 0.0066 0.0038 0.0086 -2.750
30 0.037 0.0055 0.0031 0.0071 -2.083
32 0.030 0.0045 0.0026 0.0059 -2.383
34 0.025 0.0038 0.0022 0.0049 -2.569
36 0.021 0.0031 0.0018 0.0041 -2.853
38 0.017 0.0026 0.0015 0.0034 -2.552
40 0.014 0.0021 0.0012 0.0028 -2.770
42 0.012 0.0018 0.0010 0.0023 -2.597
44 0.010 0.0015 0.0008 0.0019 -2.503
46 0.008 0.0012 0.0007 0.0016 -2.088
48 0.007 0.0010 0.0006 0.0013 -2.704
50 0.006 0.0008 0.0005 0.0011 -2.440
52 0.005 0.0007 0.0004 0.0009 -2.766
54 0.004 0.0006 0.0003 0.0007 -2.460
56 0.003 0.0005 0.0003 0.0006 -2.491
58 0.003 0.0004 0.0002 0.0005 -2.339
60 0.002 0.0003 0.0011 0.0003 -2.605

This experiment had significant causes of error may
may have been due to the type of sucrose used. Before
making some assumptions to correct the data, it appeared to
be linear. It could be that having both D and L enantiometers
of sucrose caused the values of concentration to cancel out,
making the shape of a 'V' at different stages of the reaction.
However, after assuming that the water blank is correct, the
data had to be further corrected. Another assumption is that
the concentration of the sucrose would approach 0, and
therefore the concentration would always be positive. If it
were negative, the natural log would result in an error. The
final assumption was that the reaction order is 1st order so
the angles were corrected as shown in table 2.2. In addition,
another possible error is that the concentration of HCl may
not have been 6M. It could have been 1M. Using 1M HCl
would have a tremendously slow reaction which resulted in
sucrose concentration that changed after a few minutes into
the reaction. The initial reaction rate was then extrapolated
further so that the concentration would approach 0 in a time
of 60 minutes. After applying some correction assumptions,
the data appeared relatively accurate.
Conclusion
This report demonstrated that reaction rate
decreased with increased time. The calculated specific
rotation was to determined to be close to the reference
(~66.5). In addition, the graph of concentration of sucrose vs.
time had a clear exponential decay trend. The objectives of
this lab were also to learn how to use a polarimeter to
measure the angles of rotation in addition to being able to
being able to being very good at timing the recording with the
rotation (otherwise there was huge error in the angle values).
Reaction order was determined to be one from the linearity
of the graph. The error values were very low for slope
(~0.007) and y-intercept (~0.1). In addition the 95%
confidence intervals were also relatively small (~0.01 for
slope and ~0.2 for -int) and R^2 values were greater than 0.9.
The raw data had errors possibly due to a mistake in the acid
concentration however, from the initial rate, the correct
values of concentration were extrapolated and reliable data
was obtained.










REFERENCES
1. CRC. Handbook of Chemistry and Physics: 84th Edition,
2004, pp 5-103.
2.Colby. Inversion of Sucrose.
http://www.colby.edu/chemistry/PChem/lab/InversionSucros
e.pdf (accessed April 3, 2014).
3.ResearchGate. Kinetic Modeling of the Hydrolysis of
Sucroseby Invertase.
http://www.researchgate.net/publication/18032359_Kinetic_
modeling_of_the_hydrolysis_of_sucrose_by_invertase/file/3
deec517d968fd6be5.pdf (accessed April 2, 2014).